WO2001018122A1 - Polymer-modified asphalt emulsion - Google Patents

Polymer-modified asphalt emulsion Download PDF

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Publication number
WO2001018122A1
WO2001018122A1 PCT/US2000/024388 US0024388W WO0118122A1 WO 2001018122 A1 WO2001018122 A1 WO 2001018122A1 US 0024388 W US0024388 W US 0024388W WO 0118122 A1 WO0118122 A1 WO 0118122A1
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WO
WIPO (PCT)
Prior art keywords
emulsion
approximately
percent
asphalt
weight
Prior art date
Application number
PCT/US2000/024388
Other languages
French (fr)
Inventor
Wayne Harlan
Original Assignee
J.S.G. Enterprises, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by J.S.G. Enterprises, Inc. filed Critical J.S.G. Enterprises, Inc.
Priority to AU73507/00A priority Critical patent/AU7350700A/en
Priority to US09/778,317 priority patent/US20020058734A1/en
Publication of WO2001018122A1 publication Critical patent/WO2001018122A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C08L95/005Aqueous compositions, e.g. emulsions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05Stirrers
    • B01F27/11Stirrers characterised by the configuration of the stirrers
    • B01F27/115Stirrers characterised by the configuration of the stirrers comprising discs or disc-like elements essentially perpendicular to the stirrer shaft axis
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04Rosin

Definitions

  • the present invention relates to polymer-modified asphalt emulsions, and a method and apparatus to make and use the asphalt emulsions for repairing roads and pavement More particularly, the invention relates to stable, asphalt polymer compositions that can be applied at ambient temperatures
  • the polymer is added for the purpose of reducing the heat sensitivity of the asphalt by increasing or extending the plasticity range, and increasing the resistance to deformation and the breaking point. It has also been shown that the performance of a properly selected asphalt polymer composition is superior to that of an asphalt not containing an added polymer. However, the problems of constituent compatibility encountered in attempts to obtain the best compromise between the performance and storage stability are difficult to overcome.
  • European Patent EP458386 relates to a process for obtaining an asphalt polymer composition that is stable under conditions of fluidity prevailing during hot storage.
  • the process consists of mixing at a temperature of 200 to 250°C, 85 to 98 weight percent of a selected asphalt, and 15 to 2 weight percent of a sequenced styrene/butadiene/styrene copolymer (SBS).
  • SBS sequenced styrene/butadiene/styrene copolymer
  • Common practice is to add the desired level of a single polymer, and a cross-linking agent, such as sulfur, until the desired asphalt properties are met.
  • a cross-linking agent such as sulfur
  • the relatively high cost of the polymer adds significantly to the overall cost of the resulting asphalt/polymer mix.
  • Grubba U.S. Patent No. 5,795,929 appears to have overcome the high polymer/asphalt ratio and the incompatibility problems associated with prior polymer-modified asphalt emulsions.
  • Grubba found that when sulfur is added as a cross-linking agent to an asphalt mixture containing both radial and linear styrene-diene copolymers (total 0.5-20 wt.%) significant property enhancements occur. Interestingly, no property enhancements were found in the absence of added sulfur. Asphalt emulsions can also be prepared utilizing Grubba's polymer modified mixture.
  • polymer- modified asphalt emulsions were prepared consisting of 60 to 80% asphalt polymer to 40 to 20% water, respectively, and an emulsifying agent
  • One disadvantage of the Grubba process is the need for an emulsification mill
  • the emulsification mill operates at temperatures between 190° F to about 210°F, and slices the asphalt-polymer mix finely to mix it with the water to form the emulsion
  • the present invention does not require an emulsification mill, and the polymer modified asphalt emulsion can be prepared at ambient temperatures
  • Asphalt emulsions are desirable in many applications because of improved handling and application at temperatures lower than hot/mix asphalt resulting from the presence of an asphalt solvent or earner phase, for example, water
  • hot/mix asphalt, and combinations of asphalt, aggregate and a single polymer are commonly heated to and applied at, a temperature of 350-450°F to achieve the requisite plasticity
  • an asphalt emulsion is typically heated to, and applied at, temperatures between 130-170°F to achieve the same working characte ⁇ stics
  • a basic emulsification requires three components asphalt, a carrier phase (e g , water) and an emulsifying agent
  • a typical emulsion is formed through addition of asphalt, any desired performance-enhancing additives, an emulsifying agent and about 20-40 weight percent of water
  • the water evaporates, leaving the asphalt structurally bound to the aggregate or other paving matenal
  • One advantage of water-based emulsified asphalt products is that they do not use or release volatile organic compounds in quantities associated with hot-mix asphalt
  • Hot-mix asphalt is generally diluted with hydrocarbon solvents such as diesel fuel or naphtha to improve the workability of the product during application
  • emulsifier employed is determined by the desired application of the asphalt emulsion In the case of rapid-set emulsions (mainly used for repair work of old pavement), the emulsion is applied on the existing surface and aggregate is spread on top After the water from the emulsion has evaporated, an intimate mixture of asphalt and stone with good load- bearing capacity is formed.
  • anionic emulsions and cationic emulsions While nonionic emulsions also exist, they are used less frequently than anionic and cationic emulsions.
  • anionic emulsion lies in the relatively low cost of the emulsifying agents.
  • the quality of the road surface is generally dependent upon the strength of the bonds between the asphalt and the aggregate after curing of the composition. Poor surface performance is due to poor adhesion, which results in asphalt stripping off the aggregate surface.
  • Asphalt compositions also have relatively poor adhesion to aggregate in the presence of water, because the aggregate prefers to be wetted by the water rather than the asphalt. As a result, the water in the emulsion interferes with the bond between the aggregate and the asphalt. The result is the formation of potholes.
  • To reduce water-induced debonding of asphalt from the stone surface it is common to add surface-active amines or diamines to the asphalt.
  • the patent literature sets forth a large number of compounds that can be used to improve adhesion of asphalt to aggregate. See, e.g., Schilling, U.S. Patent No. 5,667,578.
  • the present invention provides a polymer-enhanced asphalt that can be applied at ambient temperature.
  • the present invention also provides an improved mechanical stirring apparatus.
  • the present invention is directed to a polymer-modified asphalt emulsion and a mixing/stirring/blending apparatus particularly useful for road and pavement repairs and potholes.
  • the polymer-modified asphalt emulsion comprises bitumen, a block copolymer comprising styrene, a rosin ester and a cationic asphalt emulsion.
  • the mixture can be applied at ambient temperature.
  • the preferred block copolymer comprising styrene is styrene-butadiene-styrene (SBS), although other block copolymers may be utilized in accordance with the invention.
  • SBS styrene-butadiene-styrene
  • the block copolymer may be present in powdered form
  • the emulsion preferably compnses between approximately 0 5 and 20 percent by weight of SBS and most preferably between approximately 2 and 15 percent by weight of SBS
  • the bitumen preferably has a petroleum asphalt pen number of 10mm penetration
  • the emulsion preferably compnses between approximately 2 and 6 percent by weight bitumen and most preferably between approximately 4 and 5 percent by weight bitumen
  • the rosin preferably compnses a high acid number and is preferably dime ⁇ zed
  • the emulsion preferably comprises between approximately 0 02 and 2 percent by weight rosin and most preferably between approximately 1 and 2 percent by weight rosin
  • the emulsion preferably compnses between approximately 20 and 40 percent by weight of water and most preferably between approximately 30 and 35 percent by weight of water
  • the cationic asphalt emulsion preferably comprises an amine, such as a quatenary amine and an emulsifying agent, such as amines, primary amines, diamines, quatenary amines, imidazolene amines and combinations thereof
  • Preferred emulsifying agents include, but are not limited to, imidazoline dodecyl phenol, quatenary diamine phenol and combinations thereof
  • the emulsion preferably compnses between approximately 50 and 80 percent by weight of cationic emulsion and most preferably between approximately 60 and 70 percent by weight of cationic emulsion
  • the emulsion further comprises an additional amine which is added to the bitumen/rosin reaction
  • the emulsion preferably compnses between approximately 0 2 and 0 3 percent by weight
  • the preferred additional amine is ditaloamine
  • the invention further comprises a method of making a polymer-enhanced asphalt emulsion, comp ⁇ sing a) mixing a block copolymer composing styrene, rosin, and bitumen, b) heating the block copolymer/rosin/bitumen mixture, and c) mixing the block copolymer/rosin/bitumen mixture with cationic asphalt emulsion
  • the block copolymer and rosin are mixed to form a dry mixture and then this dry mixture is added to the bitumen
  • the block copolymer may be powdered
  • compositions and reactants are discussed above
  • the mixture may be applied at ambient temperature to the surface being repaired
  • the present invention also is directed to a mixer/stirrer/blender apparatus comprising a shaft, a plate or blade with at least one opening in the blade Preferably, there are a plurality of plates (most preferably three plates), and a plurality of openings in at least two of the plates Preferably there are no openings in the central plate
  • the plates are preferably circular
  • the plates preferably comprise an approximately five-inch radius
  • each opening in the plates are preferably circular
  • each opening is spaced at a ninety-degree angle from its neighboring opening with respect to a center of the plate, centers of the four openings are located at a point approximately seventy percent of a distance from a center of the plate to an edge of the plate, and a radius of each of the four openings is approximately twenty percent of a distance from a center of the plate to an edge of the plate
  • spacers on the shaft interposed between the plurality of plates are preferably approximately 1/8 inch thick
  • a primary object of the present invention is to provide a polymer-enhanced asphalt that can be applied at ambient temperature to selected aggregate to pave or repair roads, pavement or other surfaces
  • a further object of the invention is to provide an asphalt emulsion with improved characteristics for handling, storage, and application
  • a further object of the invention is to provide an asphalt emulsion that is applied at ambient temperatures with minimal release of volatile organic compounds (VOC) into the environment
  • Another object of the invention is to provide an improved stir ⁇ ng/mixing/blending apparatus
  • Fig. 1 is a diagram of one of the outer stirrer blades of the mechanical stirring apparatus of the invention
  • Fig. 2 is a component diagram of the mechanical stirring apparatus
  • Fig. 3 is a chemical structural representation of the rosin (Sylvaros PR 295), a dimer rosin ester, free acid hydrogen, molecular weight 480, preferably used in the emulsification process of the invention.
  • the present invention is of a polymer-enhanced asphalt emulsion comprising bitumen (e.g., bitumen (AC-10) from Frontier, Cheyenne, Wyoming wherein the 10 stands for a petroleum asphalt pen number of 10 for a 10mm penetration, standard test), a block polymer comprising styrene (e.g. styrene-butadiene-styrene (SBS)), a rosin ester with high acid number (e.g. Sylvaros PR-295
  • SBS block polymer As used throughout the specification and claims, is intended to include all styrene containing block polymers or copolymers
  • the SBS block polymer is preferably mixed with the rosin to form a dry mixture
  • the rosin is preferably a high acid number rosin ester and preferably dimenzed
  • the rosin preferably ranges between approximately 0 02 percent by weight and 2 percent by weight, and most preferably between approximately 1 percent by weight and 2 percent by weight
  • the dry mixture is slowly added to the heated asphalt, and heated for preferably one to two hours at 300° F - 500° F
  • the heated asphalt-polymer is then added to an already prepared cationic asphalt emulsion at ambient temperature
  • the asphalt-polymer mixes almost immediately with the asphalt emulsion with no separation or incompatibility problems observed
  • the emulsion comprises some water, dependent upon the desired flow and cure characteristics of the final mixture
  • the quantity and type of emulsifying agent used are dictated by the desired use of the emulsion
  • Other molecules comprising hydroxyl groups may also be added to adjust characteristics of the emulsion
  • the quantity and type of emulsifying agent used in the present invention are consistent with existing asphalt and polymer-modified emulsions known in the art
  • Known cationic emulsifying agents that can be used in the present invention include chemical agents and clay agents
  • Chemical agents include, but are not limited to, nitrogen containing molecules, such as, but not limited to, amines, for example, but not limited to, primary amines, secondary amines, quaternary amines, monoamines, diamines and other polyamines
  • Clay agents comp ⁇ se clays, such as, but not limited to, bentonite clays and the like In particular, imidazo ne dodecyl phenol and quatenary diamine
  • the final asphalt mixture can be stored in a sealed container for at least six (6) months, perhaps longer and used as needed
  • the asphalt emulsion further comprises an additional amine, preferably a di-tallow quaternary amine, for example, but not limited to, DTDMAC (di-tallow, di-methyl ammonium chlo ⁇ de) or di-tallow amine
  • This amine is in addition to the amine in the cationic emulsion
  • This amine is added, in a small amount, to the rosin/bitumen/SBS reaction to allow particles to better or completely disperse when in the mixer apparatus of the present invention
  • the additional amine is present in an amount of preferably between approximately 0 2 percent by weight and 0 3 percent by weight
  • the invention additionally comprises methods to repair potholes and cracked pavement, especially employing the composition of the invention described above
  • An example of the method when used to repair a pot hole approximately three to four inches in depth follows The pothole is filled with approximately 3/8 inch washed silicious aggregate or other paving or surfacing material Deeper pot holes are filled with larger, washed aggregate provided that approximately 3/8 inch aggregate is layered atop the larger aggregate
  • the prepared asphalt polymer emulsion, the composition of the present invention is poured into the aggregate filled hole to a level approximately equal to that of the pavement A small amount of additional 3/8 inch aggregate may be added to the hole
  • the asphalt/aggregate mixture is cured to the point such that the mixture can be compressed and leveled with the pavement, resulting in a patch that is uniform in appearance to the unrepaired portion of the roadway pavement
  • the crack is preferably routed with a commercial pavement router to at least one (1) inch in width, cleared of loose sand or gravel, and filled
  • the invention additionally comprises a mechanical stirrer/mixer/blender that is used to mix the polymer/rosin mix with the asphalt and later used to mix the asphalt polymer mixture with the cationic asphalt emulsion.
  • the stirrer preferably comprises a shaft 10, a plurality of stirrer blades 14, and a plurality of spacers 12.
  • the shaft 10 may be disposed in any container (e.g. a 55-gallon drum) for conducting the mixing on site.
  • An electric drill can be used to drive the shaft 10.
  • the stirrer preferably has three stirrer blades.
  • the blades are preferably approximately 1/4 inch thick and preferably disposed on top of each other with 1/8 inch washers or spacers.
  • a useful material for the blade is aluminum, but other materials may be utilized.
  • the blades are preferably circular with a radius of approximately five (5) inches.
  • the stirrer blades are attached to one end of the shaft 10.
  • Each outer blade 14 preferably has circular openings 16 (e.g. four openings), ninety degrees from one another, that are preferably centered 3 1/2 inches from the center of the blade 18.
  • the diameter of the openings is approximately 2 inches.
  • circular openings are shown in the drawings, oval openings could be utilized.
  • the purpose of circular or oval openings is to avoid shear.
  • An opening of sharp edges e.g. square openings
  • Radial velocity is used to achieve the pumping and stirring of the mixture.
  • the blades may have more or less than four openings. Industnal Applicability
  • Bitumen 43 lbs , AC-10, Frontier, Cheyenne, Wyoming was heated to a temperature of between approximately 300° F and 500° F Powdered SBS with a typical molecular weight (M w ) of 1 to 1 5 million (8 6 lbs , 31/69 S/B ratio, Dexco Polymers, Houston Texas) was mixed with a rosin- ester with high acid number (0 45 lbs , Sylvaros PR 295, Arizona Chemical Co ) The polymer/rosin mixture was slowly added with gentle stirring using the mixing/stirring apparatus of the present invention to the bitumen at approximately 300° F to 500° F until all the polymer/rosin mixture was added The polymer asphalt mixture was maintained at approximately 300° F to 500° F for one to two hours and then mixed with the mixer/stirrer of the invention The heated polymer asphalt mixture was then added to approximately thirty (30) gallons of already prepared cationic asphalt emulsion at ambient temperature The polymer-asphalt emulsion was rapidly mixed (approximately
  • Example 1 The mixture of Example 1 was tested to repair a pothole After 11 months to-date, the asphalt mixture of the present invention remains in good condition, with no evidence of shrinkage, cracking, sinking or other wear
  • Example 4 The mixture of Example 4 was tested to repair a pothole After 8 months to-date, the asphalt mixture of the present invention remains in good condition, with no evidence of shrinkage, cracking, sinking or other wear
  • the preceding examples can be repeated with similar success by substituting the gene ⁇ cally or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples
  • the weight percent of SBS in the final asphalt polymer emulsion can vary from approximately 2% to approximately 20%, and the corresponding weights and volume of the other constituents adjusted accordingly

Abstract

A polymer-modified asphalt emulsion and a mixing/stirring/blending apparatus particularly useful for road and pavement repairs and potholes. The polymer-modified asphalt emulsion comprises bitumen, a block copolymer comprising styrene, a rosin ester and a cationic asphalt emulsion. The mixture can be applied at ambient temperature.

Description

POLYMER-MODIFIED ASPHALT EMULSION
CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of the filing of U S Provisional Patent Application Serial No 60/152,399, entitled Polymer-Modified Asphalt Emulsion, filed on September 3, 1999, and the specification thereof is incorporated herein by reference
BACKGROUND OF THE INVENTION Field of the Invention (Technical Field) The present invention relates to polymer-modified asphalt emulsions, and a method and apparatus to make and use the asphalt emulsions for repairing roads and pavement More particularly, the invention relates to stable, asphalt polymer compositions that can be applied at ambient temperatures
Background Art
Often conventional asphalt does not retain sufficient elasticity during use, and, also, exhibits a plasticity range which is too narrow for use in many modern applications such as road construction To overcome this problem, vanous polymers have been added to asphalt to improve physical and mechanical performance The characteristics of road asphalt and the like can be greatly improved by incorporating an elastomeπc type polymer, or a random or block copolymer of styrene and a conjugated diene Consequently, polymer-modified asphalt is routinely used in the road construction/maintenance and roofing industries Polymer-modified asphalt generally comprises styrene butadiene-based polymers, which have raised softening point, increased viscoelasti ty, enhanced strain recovery, and improved low temperature strain characteristics However, the technical challenge remains in producing a polymer modified asphalt or polymer asphalt emulsion that is stable for long periods of time, that will strongly bind to aggregate, and in the case of the emulsions, that can be easily applied at ambient temperatures The durability of road pavement is greatly enhanced by the addition of a polymer. The polymer is added for the purpose of reducing the heat sensitivity of the asphalt by increasing or extending the plasticity range, and increasing the resistance to deformation and the breaking point. It has also been shown that the performance of a properly selected asphalt polymer composition is superior to that of an asphalt not containing an added polymer. However, the problems of constituent compatibility encountered in attempts to obtain the best compromise between the performance and storage stability are difficult to overcome. European Patent EP458386 relates to a process for obtaining an asphalt polymer composition that is stable under conditions of fluidity prevailing during hot storage. The process consists of mixing at a temperature of 200 to 250°C, 85 to 98 weight percent of a selected asphalt, and 15 to 2 weight percent of a sequenced styrene/butadiene/styrene copolymer (SBS).
Polymer asphalt mixtures that are employed at the present time in heavy load applications, such as road construction and repair, often do not have the optimum characteristics at low enough polymer concentrations to consistently meet the increasing structural and workability requirements imposed on roadway structures in their construction. Common practice is to add the desired level of a single polymer, and a cross-linking agent, such as sulfur, until the desired asphalt properties are met. However, the relatively high cost of the polymer adds significantly to the overall cost of the resulting asphalt/polymer mix. Thus, it is highly advantageous to develop a polymer asphalt mix that is low in polymer concentration but still has the requisite properties. Due to the large quantities involved, cost factors weigh heavily in the practical application of any polymer asphalt mixture.
Grubba, U.S. Patent No. 5,795,929 appears to have overcome the high polymer/asphalt ratio and the incompatibility problems associated with prior polymer-modified asphalt emulsions. Grubba found that when sulfur is added as a cross-linking agent to an asphalt mixture containing both radial and linear styrene-diene copolymers (total 0.5-20 wt.%) significant property enhancements occur. Interestingly, no property enhancements were found in the absence of added sulfur. Asphalt emulsions can also be prepared utilizing Grubba's polymer modified mixture. In this case polymer- modified asphalt emulsions were prepared consisting of 60 to 80% asphalt polymer to 40 to 20% water, respectively, and an emulsifying agent One disadvantage of the Grubba process is the need for an emulsification mill The emulsification mill operates at temperatures between 190° F to about 210°F, and slices the asphalt-polymer mix finely to mix it with the water to form the emulsion The present invention does not require an emulsification mill, and the polymer modified asphalt emulsion can be prepared at ambient temperatures
Asphalt emulsions are desirable in many applications because of improved handling and application at temperatures lower than hot/mix asphalt resulting from the presence of an asphalt solvent or earner phase, for example, water For example, hot/mix asphalt, and combinations of asphalt, aggregate and a single polymer are commonly heated to and applied at, a temperature of 350-450°F to achieve the requisite plasticity In comparison, an asphalt emulsion is typically heated to, and applied at, temperatures between 130-170°F to achieve the same working characteπstics
A basic emulsification requires three components asphalt, a carrier phase (e g , water) and an emulsifying agent A typical emulsion is formed through addition of asphalt, any desired performance-enhancing additives, an emulsifying agent and about 20-40 weight percent of water Once the emulsion is applied, the water evaporates, leaving the asphalt structurally bound to the aggregate or other paving matenal One advantage of water-based emulsified asphalt products is that they do not use or release volatile organic compounds in quantities associated with hot-mix asphalt Hot-mix asphalt is generally diluted with hydrocarbon solvents such as diesel fuel or naphtha to improve the workability of the product during application
Heightened environmental awareness has stimulated increased usage of emulsified asphalt in the road-paving industry The type of emulsifier employed is determined by the desired application of the asphalt emulsion In the case of rapid-set emulsions (mainly used for repair work of old pavement), the emulsion is applied on the existing surface and aggregate is spread on top After the water from the emulsion has evaporated, an intimate mixture of asphalt and stone with good load- bearing capacity is formed There are two basic types of emulsions anionic emulsions and cationic emulsions While nonionic emulsions also exist, they are used less frequently than anionic and cationic emulsions. The advantage of anionic emulsion lies in the relatively low cost of the emulsifying agents. However, as most of the aggregates used are negatively charged, for example, quartz and granite, the electrostatic repulsion between the negatively charged asphalt emulsion and the negatively charged stones causes inferior adhesion. This results in the asphalt separating from the stones, or what is generally known as the asphalt/stripping problem. This problem is also encountered in hot/mix applications and when cutback asphalt is used.
The quality of the road surface is generally dependent upon the strength of the bonds between the asphalt and the aggregate after curing of the composition. Poor surface performance is due to poor adhesion, which results in asphalt stripping off the aggregate surface. Asphalt compositions also have relatively poor adhesion to aggregate in the presence of water, because the aggregate prefers to be wetted by the water rather than the asphalt. As a result, the water in the emulsion interferes with the bond between the aggregate and the asphalt. The result is the formation of potholes. To reduce water-induced debonding of asphalt from the stone surface, it is common to add surface-active amines or diamines to the asphalt. The patent literature sets forth a large number of compounds that can be used to improve adhesion of asphalt to aggregate. See, e.g., Schilling, U.S. Patent No. 5,667,578.
The present invention provides a polymer-enhanced asphalt that can be applied at ambient temperature. The present invention also provides an improved mechanical stirring apparatus.
SUMMARY OF THE INVENTION (DISCLOSURE OF THE INVENTION The present invention is directed to a polymer-modified asphalt emulsion and a mixing/stirring/blending apparatus particularly useful for road and pavement repairs and potholes. The polymer-modified asphalt emulsion comprises bitumen, a block copolymer comprising styrene, a rosin ester and a cationic asphalt emulsion. The mixture can be applied at ambient temperature.
The preferred block copolymer comprising styrene is styrene-butadiene-styrene (SBS), although other block copolymers may be utilized in accordance with the invention. The block copolymer may be present in powdered form The emulsion preferably compnses between approximately 0 5 and 20 percent by weight of SBS and most preferably between approximately 2 and 15 percent by weight of SBS
The bitumen preferably has a petroleum asphalt pen number of 10mm penetration The emulsion preferably compnses between approximately 2 and 6 percent by weight bitumen and most preferably between approximately 4 and 5 percent by weight bitumen
The rosin preferably compnses a high acid number and is preferably dimeπzed The emulsion preferably comprises between approximately 0 02 and 2 percent by weight rosin and most preferably between approximately 1 and 2 percent by weight rosin
The emulsion preferably compnses between approximately 20 and 40 percent by weight of water and most preferably between approximately 30 and 35 percent by weight of water
The cationic asphalt emulsion preferably comprises an amine, such as a quatenary amine and an emulsifying agent, such as amines, primary amines, diamines, quatenary amines, imidazolene amines and combinations thereof Preferred emulsifying agents include, but are not limited to, imidazoline dodecyl phenol, quatenary diamine phenol and combinations thereof The emulsion preferably compnses between approximately 50 and 80 percent by weight of cationic emulsion and most preferably between approximately 60 and 70 percent by weight of cationic emulsion
In an alternative embodiment, the emulsion further comprises an additional amine which is added to the bitumen/rosin reaction The emulsion preferably compnses between approximately 0 2 and 0 3 percent by weight The preferred additional amine is ditaloamine
The invention further comprises a method of making a polymer-enhanced asphalt emulsion, compπsing a) mixing a block copolymer composing styrene, rosin, and bitumen, b) heating the block copolymer/rosin/bitumen mixture, and c) mixing the block copolymer/rosin/bitumen mixture with cationic asphalt emulsion
In the preferred embodiment, the block copolymer and rosin are mixed to form a dry mixture and then this dry mixture is added to the bitumen The block copolymer may be powdered
The preferred compositions and reactants are discussed above The mixture may be applied at ambient temperature to the surface being repaired
The present invention also is directed to a mixer/stirrer/blender apparatus comprising a shaft, a plate or blade with at least one opening in the blade Preferably, there are a plurality of plates (most preferably three plates), and a plurality of openings in at least two of the plates Preferably there are no openings in the central plate The plates are preferably circular For certain applications (e g use in a 55-gallon drum), the plates preferably comprise an approximately five-inch radius
The openings in the plates are preferably circular Preferably, there are four openings in each plate (that has openings) Preferably, each opening is spaced at a ninety-degree angle from its neighboring opening with respect to a center of the plate, centers of the four openings are located at a point approximately seventy percent of a distance from a center of the plate to an edge of the plate, and a radius of each of the four openings is approximately twenty percent of a distance from a center of the plate to an edge of the plate
There are spacers on the shaft interposed between the plurality of plates These spacers are preferably approximately 1/8 inch thick
The apparatus prevents shear of the mixture being processed A primary object of the present invention is to provide a polymer-enhanced asphalt that can be applied at ambient temperature to selected aggregate to pave or repair roads, pavement or other surfaces
A further object of the invention is to provide an asphalt emulsion with improved characteristics for handling, storage, and application
A further object of the invention is to provide an asphalt emulsion that is applied at ambient temperatures with minimal release of volatile organic compounds (VOC) into the environment
Another object of the invention is to provide an improved stirπng/mixing/blending apparatus
A primary advantage of the present invention is the storabi ty of the polymer-enhanced asphalt emulsion
Another advantage of the present advantage is the high degree of bonding between the asphalt emulsion and the aggregate
Another advantage of the present advantage is that the mixture can be varied over a wide compositional range depending on the application
Another advantage of the present invention is the uniform appearance of the asphalt- aggregate patch to the unrepaired portion of the road or pavement
Other objects, advantages and novel features, and further scope of applicability of the present invention will be set forth in part in the detailed description to follow taken in conjunction with the accompanying drawings, and in part will become apparent to those skilled in the art upon examination of the following, or may be learned by practice of the invention The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the specification below.
BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated into and form a part of the specification, illustrate several embodiments of the present invention and, together with the description, serve to explain the principles of the invention. The drawings are only for the purpose of illustrating a preferred embodiment of the invention and are not to be construed as limiting the invention. In the drawings:
Fig. 1 is a diagram of one of the outer stirrer blades of the mechanical stirring apparatus of the invention;
Fig. 2 is a component diagram of the mechanical stirring apparatus; and
Fig. 3 is a chemical structural representation of the rosin (Sylvaros PR 295), a dimer rosin ester, free acid hydrogen, molecular weight 480, preferably used in the emulsification process of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
(BEST MODES FOR CARRYING OUT THE INVENTION) The present invention is of a polymer-enhanced asphalt emulsion comprising bitumen (e.g., bitumen (AC-10) from Frontier, Cheyenne, Wyoming wherein the 10 stands for a petroleum asphalt pen number of 10 for a 10mm penetration, standard test), a block polymer comprising styrene (e.g. styrene-butadiene-styrene (SBS)), a rosin ester with high acid number (e.g. Sylvaros PR-295
(chemical structure illustrated in Fig. 3) from Arizona Chemical Company, Panama City, Florida), and a cationic asphalt emulsion. Of course, other types of styrene containing block polymers known in the art may be suitable in lieu of or in addition to SBS block copolymers, for example, but not limited to styrene-ethylene-butylene-styrene (SBES) block copolymer. The term "SBS block polymer", as used throughout the specification and claims, is intended to include all styrene containing block polymers or copolymers
As used throughout the specification and claims, the terms "bitumen" and "asphalt" are used interchangeably The SBS block polymer is preferably mixed with the rosin to form a dry mixture
The rosin is preferably a high acid number rosin ester and preferably dimenzed The rosin preferably ranges between approximately 0 02 percent by weight and 2 percent by weight, and most preferably between approximately 1 percent by weight and 2 percent by weight
The dry mixture is slowly added to the heated asphalt, and heated for preferably one to two hours at 300° F - 500° F The heated asphalt-polymer is then added to an already prepared cationic asphalt emulsion at ambient temperature With the specialized mixer blade of the invention, the asphalt-polymer mixes almost immediately with the asphalt emulsion with no separation or incompatibility problems observed
The emulsion comprises some water, dependent upon the desired flow and cure characteristics of the final mixture The quantity and type of emulsifying agent used are dictated by the desired use of the emulsion Other molecules comprising hydroxyl groups may also be added to adjust characteristics of the emulsion The quantity and type of emulsifying agent used in the present invention are consistent with existing asphalt and polymer-modified emulsions known in the art Known cationic emulsifying agents that can be used in the present invention include chemical agents and clay agents Chemical agents include, but are not limited to, nitrogen containing molecules, such as, but not limited to, amines, for example, but not limited to, primary amines, secondary amines, quaternary amines, monoamines, diamines and other polyamines Clay agents compπse clays, such as, but not limited to, bentonite clays and the like In particular, imidazo ne dodecyl phenol and quatenary diamine phenol are used separately or in combination The cationic emulsion preferably ranges between 50-80 percent by weight, and most preferably between approximately 60-70 percent by weight For the present invention, the amount of water in the final polymer-modified asphalt emulsion preferably ranges between approximately 20 and 40 percent by weight and most preferably approximately 32 percent by weight The preferred weight percent of SBS in the final asphalt polymer emulsion preferably ranges between approximately 2 percent by weight and 20 percent by weight, and most preferably approximately between approximately 2 percent by weight and 15 percent by weight
The final asphalt mixture can be stored in a sealed container for at least six (6) months, perhaps longer and used as needed
In an alternative embodiment, the asphalt emulsion further comprises an additional amine, preferably a di-tallow quaternary amine, for example, but not limited to, DTDMAC (di-tallow, di-methyl ammonium chloπde) or di-tallow amine This amine is in addition to the amine in the cationic emulsion This amine is added, in a small amount, to the rosin/bitumen/SBS reaction to allow particles to better or completely disperse when in the mixer apparatus of the present invention The additional amine is present in an amount of preferably between approximately 0 2 percent by weight and 0 3 percent by weight
The invention additionally comprises methods to repair potholes and cracked pavement, especially employing the composition of the invention described above An example of the method when used to repair a pot hole approximately three to four inches in depth follows The pothole is filled with approximately 3/8 inch washed silicious aggregate or other paving or surfacing material Deeper pot holes are filled with larger, washed aggregate provided that approximately 3/8 inch aggregate is layered atop the larger aggregate The prepared asphalt polymer emulsion, the composition of the present invention, is poured into the aggregate filled hole to a level approximately equal to that of the pavement A small amount of additional 3/8 inch aggregate may be added to the hole After approximately twenty to thirty minutes the asphalt/aggregate mixture is cured to the point such that the mixture can be compressed and leveled with the pavement, resulting in a patch that is uniform in appearance to the unrepaired portion of the roadway pavement As to cracked pavement, for pavement cracks less than approximately one (1) inch in width, the crack is preferably routed with a commercial pavement router to at least one (1) inch in width, cleared of loose sand or gravel, and filled with approximately 1/8 to 1/4 inch washed silicious aggregate. The fill step is repeated as in the case of repairing the pothole, above.
Referring to Figs. 1 and 2, the invention additionally comprises a mechanical stirrer/mixer/blender that is used to mix the polymer/rosin mix with the asphalt and later used to mix the asphalt polymer mixture with the cationic asphalt emulsion. This facilitates the mixing of these respective components to a point achieving approximate homogeneity. The stirrer preferably comprises a shaft 10, a plurality of stirrer blades 14, and a plurality of spacers 12. The shaft 10 may be disposed in any container (e.g. a 55-gallon drum) for conducting the mixing on site. An electric drill can be used to drive the shaft 10.
The stirrer preferably has three stirrer blades. The blades are preferably approximately 1/4 inch thick and preferably disposed on top of each other with 1/8 inch washers or spacers. A useful material for the blade is aluminum, but other materials may be utilized. The blades are preferably circular with a radius of approximately five (5) inches. The stirrer blades are attached to one end of the shaft 10. Each outer blade 14 preferably has circular openings 16 (e.g. four openings), ninety degrees from one another, that are preferably centered 3 1/2 inches from the center of the blade 18. Preferably, the diameter of the openings is approximately 2 inches.
Although circular openings are shown in the drawings, oval openings could be utilized. The purpose of circular or oval openings is to avoid shear. When the liquid enters the hole, it acts as a pump and pumps the liquid over the surface of the blade. An opening of sharp edges (e.g. square openings) may cause shear. Radial velocity is used to achieve the pumping and stirring of the mixture. Likewise the blades may have more or less than four openings. Industnal Applicability
The invention is further illustrated by the following non-limiting examples
Example 1 (3 0% SBS)
Bitumen (43 lbs , AC-10, Frontier, Cheyenne, Wyoming) was heated to a temperature of between approximately 300° F and 500° F Powdered SBS with a typical molecular weight (Mw) of 1 to 1 5 million (8 6 lbs , 31/69 S/B ratio, Dexco Polymers, Houston Texas) was mixed with a rosin- ester with high acid number (0 45 lbs , Sylvaros PR 295, Arizona Chemical Co ) The polymer/rosin mixture was slowly added with gentle stirring using the mixing/stirring apparatus of the present invention to the bitumen at approximately 300° F to 500° F until all the polymer/rosin mixture was added The polymer asphalt mixture was maintained at approximately 300° F to 500° F for one to two hours and then mixed with the mixer/stirrer of the invention The heated polymer asphalt mixture was then added to approximately thirty (30) gallons of already prepared cationic asphalt emulsion at ambient temperature The polymer-asphalt emulsion was rapidly mixed (approximately 300 to 600 rpm) with the mixer/stirrer for ten minutes
Example 2 (4 0% SBS)
The same preparation method was used as described for Example 1 for the corresponding amounts of matenals
Bitumen 43 lbs
SBS 12 5 lbs
Rosin 0 625 lbs
Asphalt Emulsion 30 gallons Example 3 (5 0% SBS)
The same preparation method was used as described for Example 1 for the corresponding amounts of mateπals Bitumen 43 lbs
SBS 17 2 lbs
Rosin 0 96 lbs
Asphalt Emulsion 30 gallons
Example 4 (6 0% SBS)
The same preparation method was used as described for Example 1 for the corresponding amounts of mateπals
Bitumen 50 lbs
SBS 19 0 lbs Rosin 1 0 lbs
Asphalt Emulsion 30 gallons
Example 5
The mixture of Example 1 was tested to repair a pothole After 11 months to-date, the asphalt mixture of the present invention remains in good condition, with no evidence of shrinkage, cracking, sinking or other wear
Example 6
The mixture of Example 4 was tested to repair a pothole After 8 months to-date, the asphalt mixture of the present invention remains in good condition, with no evidence of shrinkage, cracking, sinking or other wear
The preceding examples can be repeated with similar success by substituting the geneπcally or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples In particular, the weight percent of SBS in the final asphalt polymer emulsion can vary from approximately 2% to approximately 20%, and the corresponding weights and volume of the other constituents adjusted accordingly
Although the invention has been described in detail with particular reference to these preferred embodiments, other embodiments can achieve the same results Vaπations and modifications of the present invention will be obvious to those skilled in the art and it is intended to cover in the appended claims all such modifications and equivalents The entire disclosures of all references, applications, patents, and publications cited above are hereby incorporated by reference

Claims

What is claimed is
1 A polymer-enhanced asphalt emulsion comprising bitumen, a block copolymer comprising styrene, rosin, and cationic asphalt emulsion, and preferably wherein said bitumen comprises bitumen with a petroleum asphalt pen number of 10mm penetration, and preferably wherein said rosin comprises a high acid number, and preferably wherein said rosin is dimenzed, and preferably wherein said cationic asphalt emulsion compnses an amine and most preferably a quatenary amine
2 The emulsion of claim 1 wherein said block copolymer comprising styrene comprises styrene-butadiene-styrene (SBS)
3 The emulsion of claim 1 comprising between approximately 2 and 6 percent by weight bitumen, and preferably compnsmg between approximately 4 and 5 percent by weight bitumen
4 The emulsion of claim 1 comprising between approximately 0 02 and 2 percent by weight rosin, and preferably comprising between approximately 1 and 2 percent by weight rosin
5 The emulsion of claim 1 comprising between approximately 20 and 40 percent by weight of water, and preferably compnsmg between approximately 30 and 35 percent by weight of water 6 The emulsion of claim 1 comprising between approximately 0 5 and 20 percent by weight of block polymer compnsmg styrene, and preferably comprising between approximately 2 and 15 percent by weight of block polymer compnsmg styrene
7 The emulsion of claim 1 wherein said cationic emulsion comprises at least one emulsifying agent selected from the group consisting of amines, primary amines, diamines, quatenary amines, imidazolene amines and combinations thereof, and preferably wherein said cationic emulsion compnses at least one emulsifying agent selected from the group consisting of imidazo ne dodecyl phenol, quatenary diamine phenol and combinations thereof
8 The emulsion of claim 1 comprising between approximately 50 and 80 percent by weight of cationic emulsion, and preferably comprising between approximately 60 and 70 percent by weight of cationic emulsion
The emulsion of claim 1 wherein said block copolymer comprises powder
10 The emulsion of claim 1 further comprising an additional amine, and preferably wherein said additional amine is added to the bitumen/rosin and preferably wherein said additional amine compnses between approximately 0 2 and 0 3 percent by weight, and preferably wherein said additional amine comprises ditaloamme
11. A method of making a polymer-enhanced asphalt emulsion, the method comprising the steps of: a) mixing block copolymer comprising styrene, rosin, and bitumen; b) heating the block copolymer/rosin/bitumen mixture; and c) mixing the block copolymer/rosin/bitumen mixture with cationic asphalt emulsion; and preferably wherein step c) comprises mixing a cationic asphalt emulsion comprising an emulsifying agent selected from the group consisting of amines, primary amines, quatenary amines, diamines, imidazolene amines and combinations thereof; and preferably wherein step c) comprises mixing a cationic asphalt emulsion comprising an emulsifying agent selected from the group consisting of imidazoline dodecyl phenol, quatenary diamine phenol and combinations thereof; and preferably wherein step c) comprises mixing using a mixer/stirrer/blender apparatus comprising a shaft, a plurality of plates attached thereto, and a plurality of openings in at least two of the plates.
12. The method of claim 11 wherein step a) comprises the steps of mixing the block copolymer and rosin to form a dry mixture and adding the dry mixture to the bitumen.
13. The method of claim 11 wherein step a) comprises mixing powdered block copolymer.
14. The method of claim 11 further comprising the step of applying the emulsion to a surface at ambient temperature. 15 An apparatus for mixing/stirπng/blending asphalt comprising a shaft, at least one plate attached to said shaft, and a plurality of openings in said at least one plate, and preferably wherein said plate(s) are circular and most preferably wherein said plate(s) comprise an approximately five-inch radius, and preferably wherein said plate(s) comprise circular openings, and preferably wherein said plate(s) comprise four openings and most preferably wherein each said opening is spaced at a ninety-degree angle from its neighboring opening with respect to a center of said plate, and more preferably wherein centers of said four openings are located at a point approximately seventy percent of a distance from a center of said plate to an edge of said plate and most preferably wherein a radius of each of said four openings is approximately twenty percent of a distance from a center of said plate to an edge of said plate, and optionally comprising a plurality of plates and a plurality of spacers on said shaft interposed between said plurality of plates, and preferably wherein said spacers are approximately 1/8 inch thick
16 The apparatus of claim 15 comprising three plates, and preferably wherein a central plate has no openings
17 The apparatus of claim 15 preventing shear of a mixture being processed
PCT/US2000/024388 1999-09-03 2000-09-05 Polymer-modified asphalt emulsion WO2001018122A1 (en)

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CN100362053C (en) * 2006-06-29 2008-01-16 重庆大学 Stone chip layer sealing composite modified emulsified asphalt and its preparation method
CN100457830C (en) * 2005-01-04 2009-02-04 同济大学 High-performance Sasobit and SBR modified emulsified asphalt, and its preparation method and uses
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WO2013163467A1 (en) * 2012-04-26 2013-10-31 Arizona Chemical Company, Llc Rejuvenation of reclaimed asphalt
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CN107619608A (en) * 2016-07-15 2018-01-23 中国石油化工股份有限公司 A kind of block copolymer-modified asphalt emulsion and preparation method thereof
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Cited By (16)

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Publication number Priority date Publication date Assignee Title
US7517934B2 (en) 2003-07-31 2009-04-14 Basf Corporation Modified anionically polymerized polymers
CN100457830C (en) * 2005-01-04 2009-02-04 同济大学 High-performance Sasobit and SBR modified emulsified asphalt, and its preparation method and uses
CN100355834C (en) * 2005-12-08 2007-12-19 广州大学 SBS modified emulsifying asphalt and preparation process thereof
CN100362053C (en) * 2006-06-29 2008-01-16 重庆大学 Stone chip layer sealing composite modified emulsified asphalt and its preparation method
WO2010125167A1 (en) * 2009-05-01 2010-11-04 Shell Internationale Research Maatschappij B.V. Styrene-butadiene composition
WO2013090283A1 (en) * 2011-12-12 2013-06-20 Arizona Chemical Company, Llc Rejuvenation of reclaimed asphalt
US10030145B2 (en) 2012-04-26 2018-07-24 Kraton Chemical, Llc Rejuvenation of reclaimed asphalt
WO2013163463A1 (en) * 2012-04-26 2013-10-31 Arizona Chemical Company, Llc Rejuvenation of reclaimed asphalt
US9828506B2 (en) 2012-04-26 2017-11-28 Kraton Chemical, Llc Rejuvenation of reclaimed asphalt
WO2013163467A1 (en) * 2012-04-26 2013-10-31 Arizona Chemical Company, Llc Rejuvenation of reclaimed asphalt
US20210054210A1 (en) * 2015-11-13 2021-02-25 Ergon Asphalt & Emulsions, Inc. Crack resistant micro surfacing composition
US11781019B2 (en) * 2015-11-13 2023-10-10 Ergon, Inc. Crack resistant micro surfacing composition
CN105331330A (en) * 2015-12-16 2016-02-17 甘肃恒达路桥工程集团有限公司中心试验室 Ultraviolet-resistant bituminous pavement crack filling glue and preparation method thereof
CN105331330B (en) * 2015-12-16 2016-08-24 甘肃恒达路桥工程集团有限公司中心试验室 The asphalt pavement crack sealing of resistance to ultraviolet glue and preparation method thereof
CN107619608A (en) * 2016-07-15 2018-01-23 中国石油化工股份有限公司 A kind of block copolymer-modified asphalt emulsion and preparation method thereof
CN107619608B (en) * 2016-07-15 2021-06-04 中国石油化工股份有限公司 Block copolymer modified asphalt emulsion and preparation method thereof

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